EP0270963A1 - Trihalogénométhyl-5 isoxazoles contenant du fluor et leur procédé de préparation - Google Patents

Trihalogénométhyl-5 isoxazoles contenant du fluor et leur procédé de préparation Download PDF

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Publication number
EP0270963A1
EP0270963A1 EP87117652A EP87117652A EP0270963A1 EP 0270963 A1 EP0270963 A1 EP 0270963A1 EP 87117652 A EP87117652 A EP 87117652A EP 87117652 A EP87117652 A EP 87117652A EP 0270963 A1 EP0270963 A1 EP 0270963A1
Authority
EP
European Patent Office
Prior art keywords
isoxazole
hydrogen fluoride
mol
fluorinating agent
isoxazoles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP87117652A
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German (de)
English (en)
Other versions
EP0270963B1 (fr
Inventor
Bernd Dr. Baasner
Alexander Dr. Klausener
Pieter Dr. Ooms
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
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Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0270963A1 publication Critical patent/EP0270963A1/fr
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Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
    • C07D261/08—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms

Definitions

  • the present invention relates to new 5-trihalomethyl isoxazoles of the formula (I) in the x stands for 1, 2 or 3.
  • Formula (I) comprises the following individual compounds: 5-trifluoromethyl isoxazole, 5-difluorochloromethyl isoxazole and 5-fluorodichloromethyl isoxazole.
  • the present invention further relates to a process for the preparation of 5-trihalomethyl isoxazoles of the formula (I) in the x represents 1, 2 or 3, which is characterized in that 5-trichloromethyl isoxazole is reacted with a fluorinating agent.
  • fluorinating agents are hydrogen fluoride and antimony trifluoride.
  • Anhydrous hydrogen fluoride is preferably used.
  • the 5-trichloromethyl isoxazole required as starting material for the process according to the invention and its preparation are known (see DE-OS 32 12 137).
  • 5-difluorochloromethyl- and 5-trifluoromethyl-isoxazole according to the invention not only 5-trichloromethyl-isoxazole can be assumed, but also 5-fluorodichloromethyl-isoxazole or mixtures thereof with 5-trichloromethyl-isoxazole.
  • 5-difluorochloromethyl-isoxazole or mixtures thereof with 5-fluorodichloromethyl-isoxazole and / or 5-trichloromethyl-isoxazole can also be used.
  • hydrogen fluoride is used as the fluorinating agent, this is preferably used in a large stoichiometric excess, since the excess can then serve as a solvent.
  • you can pro Use 3 to 1,500 moles of hydrogen fluoride, in particular anhydrous hydrogen fluoride, in moles of starting material ( 5-trichloromethyl and / or 5-fluorodichloromethyl and / or 5-difluorochloromethyl isoxazole).
  • antimony trifluoride is used as the fluorinating agent, it is possible, for example, to use the stoichiometrically required amount or an excess of up to 30 mol%, and in the case of the production of 5-trifluoromethyl isoxazole, an excess of up to 200 mol%.
  • Other fluorinating agents can be used, for example, in appropriate amounts, such as antimony trifluoride.
  • the fluorination according to the invention can optionally be carried out in the presence of customary fluorination catalysts, as described, for example, in Houben-Weyl, Methods of Organic Chemistry, Georg-Thieme-Verlag, Stuttgart, Vol. 5/3, pp. 124 ff. (1962).
  • Antimony pentachloride, mixtures and / or reaction products of antimony trichloride and / or antimony trifluoride with chlorine and / or hydrogen fluoride are particularly suitable.
  • Such reaction products can correspond, for example, to the formula (II) SbCl n F 5-n (II), in the n represents an integer or fractional number from 1 to 5.
  • Antimony pentachloride is preferably used. If fluorination catalysts are used, this can be done, for example, in amounts of 0.005 to 1 mol per mol of starting compound.
  • the fluorination according to the invention is generally carried out at elevated temperature.
  • the pressure can be selected, for example, in the range from 1 to 50 bar.
  • hydrogen fluoride as the fluorinating agent
  • an inert gas e.g. Nitrogen
  • the process is preferably carried out at normal pressure or pressures up to 5 bar.
  • Suitable reaction times when using hydrogen fluoride as the fluorinating agent are, for example, those in the range from 1 to 24 hours.
  • the process according to the invention can also be carried out continuously, it being possible for the fluorination to be carried out, for example, with anhydrous hydrogen fluoride in a corresponding reactor in the gas phase.
  • Both reactants eg 5-trichloromethyl isoxazole and hydrogen fluoride
  • pressures up to 50 bar can prevail.
  • reaction times given above can also be chosen to be shorter and, for example, between 0.1 and 10, particularly preferably between 0.5 and 5, hours in all production processes.
  • the process according to the invention can be carried out, for example, in such a way that 5-trichloromethyl isoxazole and the respective fluorinating agent, if appropriate together with a fluorinating catalyst, at room temperature or with cooling (the latter in particular when using hydrogen fluoride as the fluorinating agent), optionally setting a pre-pressure with nitrogen, then heating to the reaction temperature, cooling again after the end of the reaction, when in use closed reaction vessels, the hydrogen chloride formed is released and the reaction mixture is worked up.
  • This work-up can be carried out, for example, by first removing excess fluorinating agent and any fluorination catalyst present, for example by distillation and / or washing with water, and then fractionating the crude product thus obtained at normal or reduced pressure.
  • reaction mixture can also be worked up in another way, for example by adding water (if appropriate only after the removal of hydrogen fluoride), separating the organic phase, washing the aqueous phase with an inert organic solvent and fractionating the combined organic phases at normal or reduced Print.
  • the new 5-trihalomethyl isoxazoles of the formula (I) in the x represents 1, 2 or 3, are valuable intermediates from which, for example, crop protection agents, pharmaceuticals and dyes can be produced.
  • the NMR measurements were carried out on a Bruker WP 80 FT spectrometer with a 1H / 19F dual probe head at a measurement frequency of 80 MHz (for 1H) and 75.39 MHz (for 19F).
  • the mass spectrographic data were determined on a Finnigan MAT 112 type mass spectrometer (EI-mode, 70 eV).
  • the following table shows the NMR data and the main peaks of the mass spectra.
  • test animals The condition of the test animals was checked 3 days after starting the experiments. This test showed a superior effect of the active ingredient over the prior art.
  • test animals The condition of the test animals was continuously checked. The time was determined which is necessary for a 100% knock-down effect. This test showed a superior effect of the active ingredient over the prior art.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)
EP87117652A 1986-12-12 1987-11-28 Trihalogénométhyl-5 isoxazoles contenant du fluor et leur procédé de préparation Expired - Lifetime EP0270963B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19863642453 DE3642453A1 (de) 1986-12-12 1986-12-12 Neue, fluor enthaltende 5-trihalogenmethyl-isoxazole und ein verfahren zu deren herstellung
DE3642453 1986-12-12

Publications (2)

Publication Number Publication Date
EP0270963A1 true EP0270963A1 (fr) 1988-06-15
EP0270963B1 EP0270963B1 (fr) 1991-08-07

Family

ID=6316036

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87117652A Expired - Lifetime EP0270963B1 (fr) 1986-12-12 1987-11-28 Trihalogénométhyl-5 isoxazoles contenant du fluor et leur procédé de préparation

Country Status (4)

Country Link
US (1) US4888430A (fr)
EP (1) EP0270963B1 (fr)
JP (1) JPH085868B2 (fr)
DE (2) DE3642453A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007106818A1 (fr) * 2006-03-13 2007-09-20 University Of Florida Research Foundation, Inc. Synthese d'alcynes et d'heterocycles substitues au pentafluorosulfanyle (sf5)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4000150A (en) * 1973-05-22 1976-12-28 Produits Chimiques Ugine Kuhlmann Perfluoroalkyl isoxazoles
DE2847766A1 (de) * 1977-11-07 1979-05-10 Hoffmann La Roche 2-imino-imidazolidin-derivate
DE2801579A1 (de) * 1978-01-14 1979-07-19 Basf Ag Triazolyl-glykolaether
EP0091022A1 (fr) * 1982-04-01 1983-10-12 BASF Aktiengesellschaft 5-Trichlorométhylisoxazole, procédé de préparation et utilisation
EP0192060A1 (fr) * 1985-02-04 1986-08-27 Nihon Bayer Agrochem K.K. Composés hétérocycliques

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MA19540A1 (fr) * 1981-07-17 1983-04-01 May & Baker Ltd Derives du n-phenylpyrazole
DE3212137A1 (de) * 1982-04-01 1983-10-06 Basf Ag 5-trichlormethylisoxazol und verfahren zu seiner herstellung

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4000150A (en) * 1973-05-22 1976-12-28 Produits Chimiques Ugine Kuhlmann Perfluoroalkyl isoxazoles
DE2847766A1 (de) * 1977-11-07 1979-05-10 Hoffmann La Roche 2-imino-imidazolidin-derivate
DE2801579A1 (de) * 1978-01-14 1979-07-19 Basf Ag Triazolyl-glykolaether
EP0091022A1 (fr) * 1982-04-01 1983-10-12 BASF Aktiengesellschaft 5-Trichlorométhylisoxazole, procédé de préparation et utilisation
EP0192060A1 (fr) * 1985-02-04 1986-08-27 Nihon Bayer Agrochem K.K. Composés hétérocycliques

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Band 75, Nr. 9, 30. August 1971, Columbus, Ohio, USA DEL'TSOVA, D.P.; ANANYAN, E.S; GAMBARYAN, N.P. "Trifluoroacetonitrile N-Oxide" seite 447, spalte 2, Zusammenfassung-Nr. 63 699d & Izv. Akad. Nauk SSSR, Ser. Khim. 1971, (2), 362-6 *

Also Published As

Publication number Publication date
DE3772012D1 (de) 1991-09-12
DE3642453A1 (de) 1988-06-23
JPS63156783A (ja) 1988-06-29
EP0270963B1 (fr) 1991-08-07
US4888430A (en) 1989-12-19
JPH085868B2 (ja) 1996-01-24

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